Motor fuel



United States Patent MOTOR FUEL William M. Sweeney, Hopewell Junction,and Robert Y.

Heisler, Fishkill, N.Y., assignors to Texaco Inc, a corporation ofDelaware No Drawing. Application June 8, 1&55 Serial No. 514,116

9 Claims. (Cl. 4468) This invention relates to an improved fuelcomposition containing a novel class of anti-knock agents. for motorfuel.

This invention particularly concerns. motor fuel antiknock additivescomprising the reaction products of acetylenic alcohol or its esters anddicobalt octacarbonyl. Moreover, we contemplate the addition of about0.4 gram per gallon and up to the limit of solubility of these reactionproducts to a motor fuel to form a fuel composition of improvedanti-knock rating. However, the preferred amount of additive is from 3to grams per gallon of motor fuel.

In general, acetylenic alcohols having from 3 to 20 carbon atoms areuseful in the formation of these products, however, we prefer thosehaving from 3 to 12. Some of the preferred acetylenic alcohols which areused, either as alcohols or in the form of their esters, to form thereaction products of the present invention are 2- propyn-l-ol, betterknown as propargyl alcohol, 2-methyl- 3-butyn-2-ol, E-methyl 1pentyn-3-ol, 2,5-dimethyl-3- hexyn-2,5-diol, 3,6-dimethyl 4octyn-3,6-diol and 1- ethynylcyclohexanol.

The esters which are useful in this invention are substituted orunsubstituted esters of acetylenic alcohols having the following generalformula 0 R-0IV wherein R is an alkyl or aryl radical which may or maynot be substituted with a halogen, a nitro group or an OR, R is analiphatic, hydroxy substituted aliphatic or cycloaliphatic radicalcontaining at least one acetylenic bond and R" is an aliphatic radical.The following are examples of such esters: propargyl acetate, propargyltrichloroacetate, propargyl trifluoroacetate, propargyltrichloroacrylate, propargyl benzoate, propargyl p-nitrobenzoate,propargyl 3,5-dinitrobenzoate, propargyl omethoxybenzoate, propargylrn-bromobenzoate, propargyl o-iodobenzoate, propargyl o-chlorobenzoate,1,1-dimethyl- 2-propynyl trichloroacryiate, 1,1-dimethyl-2-propynl'acetate, 1,1-dimethyl-2-propynyl p-nitrobenzoate, l-methyl-1-ethyl-2-propynyl acetate, 1,1,4-trirnethyl-4 hydroxy-2- pentynylmonotrichloroacrylate, 1,1,4,4 tetrarnethyl-2- butynylenedi-o-methoxybenzoate, 1,4-dimethyl-1-ethyl-4- hydroxy-Z-hexynylmonoacetate, 1,4-dimethyl-1,4-diethyl- Z-butynylene dibenzoate,l-ethynylcyclohexyl acetate, 1- ethynylcyclohexyl trichlcroacrylate, 1etliynylcyclohexyl m-bromobenzoate and l-ethynylcyclohexyl 3,5dinitrobenzoate. Where the esters of the present invention are formedwith aliphatic acid portions, the acid portions contain from 1 to 20carbon atoms but preferably from 1 to 6. Those halogenated aliphaticacid por-,

where R represents an alkyl or aryl radical containing at least onehalogen atom and R is an aliphatic, hydroxy substituted aliphatic orcycloaliphatic radical having at least one acetylenic bond are novelcompounds and are disclosed as such in our copending application, SerialNo. 514,117, filed of even date herewith and now abandoned.

In the formation of the compounds of this invention, two moles of carbonmonoxide are given off in accordance with the following equation usingpropargyl alcohol for an example It can be seen that a reaction productwhich might be termed propargyl alcohol dicobalt hexacarbonyl is formedalong with the two moles of carbon monoxide.

It is recognized that metal carbonyls have been used as fuel additives.However, the cobalt carbonyl reaction products of this invention aremore stable than cobalt carbonyl per se and do not require storage in anatmosphere of carbon monoxide as does cobalt carbonyl.

The reaction products of this invention, with the exception of thatformed with propargyl alcohol are novel compounds and methods of formingthem are presented in the following examples.

EXAMPLE 1 Preparation 0 propargyl trichloroacrylate dicobalthexacarbonyl 10.6 g. of propargyl trichloroacrylate, 17.1 g. of dicobaltoctacarbonyl and 250 cc. of pentane were mixed together and allowed tostand until the evolution of carbon monoxide ceased (3 hours). Themixture was filtered, solvent stripped, and a red crystalline residuecrys Preparation 0] propargyl p-nitrobenzoate dicobalt hexacarbonyl 12.6g. of propar gyl p-nitrobenzoate, 17.1 g. of dicobalt octacarbonyl and250 cc. of pentane were allowed to stand until the evolution of carbonmonoxide ceased (3 hours). The product was filtered and the precipitaterecrystallized from benzene. Yield: 12 g., 48%.

' The melting point was found to be 133 to 134 C. On analysis, thepercentage composition was as follows: C=39.3, H=1.5, N =2.8, Co=23.2,the molecular Weight=492. These values correspond closely to thetheoretical composition which is C=39.0, H: 1.4, N=2.7, Co=23.2 and themolecular weight is 492. This product also showed excellent stability onstanding in open air.

EXAMPLE 3 Preparation of propargyl benzoate dicobalt hexacarbonyl 3.4 g.of dicobalt octacarbonyl, 1.7 g. of propargyl benz oate and 20 cc. ofoctane were mixed] together and allowed to stand until the evolution ofcarbon monoxide ceased (1 hour). The mixture was filtered and thefiltrate was stripped of the solvent under reduced pressure. The redcrystalline material was recrystallized from water- ,ethanol mixture.Yield: 4 g., 93%.

The melting point of this additive was found to be 2,910,352 g H r p j 389 to 90 C. Analysis of the composition showed C=43.l, H=2.0, Co=26.7,the molecular weight=438. Again these figures closely coincide with thetheoretical values which are as follows: C=43.2, H=l.8, Co=26.5 and themolecular weight is 446. No decomposition was observed on standing inopen air.

EXAMPLE 4 Preparation of propargyl 3,5-dinitrbenzoate dicobalthexacarbonyl 10 g. of propargyl 3,5-dinitrobenzoate, 13.7 g. ofdibenzene were allowed to stand until evolution of carbon monoxideceased (3 hours). The solvents were removed and the red crystallineresidue recrystallized from ethanol. Yield: 199 g., 87.5%.

The melting point was found to be 102" C. No decomposition of thecompound was observed on standing in open air.

EXAMPLE 5 Preparation of propargyl acetate dicobalt hexacarbonyl 40 g.of propargyl acetate, 140 g. of dicobalt octacarbonyl and 300 cc. ofpentane were mixed together and allowed to stand overnight. The productwas filtered and the solvent was allowed to evaporate yielding a violetamorphous solid. Yield: 38 g., 25%.

This compound exhibited excellent stability on standing in open air.

EXAMPLE 6 Preparation of propargyl trichloroacetate dicobalthexacarbonyl 42.8 g. of dicobalt octacarbonyl, 20.2 g. of propargyltrichloroacetate and pentane as required were mixed together and allowedto stand until the carbon monoxide elimination was completed. Theproduct was filtered and the solvent was allowed to evaporate. A reddishcrystalline substance was observed.

EXAMPLE 7 Preparation of propargyl trifluoroacctate dicobalthexacarbonyl TABLE 1 ASTM Additive at 5 g. per gal. concentrationresearch octane number None 84. 5 Propargyl alcohol dicobalthcxacarbonyl 91.0 Propargyl acetate dicobalt hexacarbonyl 89. 6Propargyl trichloroacrylatc dicobalt hexacarbonyL. 85. 7 Propargylp-nitrobenzoate dicobalt hexacarbonyl... 85. 7 Propargyl bcnzcatedicobalt hexacarbonyl 85. 5

From the above table it can be seen that reaction products of acetylenicalcohols and their esters and c0- cobalt octacarbonyl, 100 cc. ofpentane and 50 cc. of

balt carbonyl have definite value as anti-knock agents in motor fuel andthe preferred products, propargyl alcohol dicobalt hexacarbonyl andpropargyl acetate dicobalt hexacarbonyl, are particularly effective.

The following table demonstrates the effectiveness of the preferredadditive propargyl alcohol dicobalt hexacarbonyl in various amounts upto its most effective concentration.

The foregoing table shows that the reaction products of this inventionhave utility in additive amounts of as little as 0.4 g. per gallon, orspecifically 0.43 g. per gallon as shown. Further, it is seen that thevalue of the compounds increases as the concentration increases up toamounts of about 3 to 5 g. per gallon. We have found that there islittle commercial value in the use of amounts over the preferred 5 g.per gallon. However, such amounts up to the limit of solubility of thereaction product in the fuel may be used.

Obviously, many modifications and variations of the invention ashereinbefore set forth, may be made without departing from the spiritand scope thereof and, therefore, only such limitations should beimposed as are indicated in the appended claims.

We claim:

1. A liquid hydrocarbon fuel boiling within the gasoline rangecontaining a reaction product of dicobalt octacarbonyl and an acetyleniccompound, in an amount sufficient to lend anti-knock properties to thefuel, said reaction product having the following general formula:

wherein R is selected from the group consisting of hydrogen, aliphaticacyl hydrocarbon, halogen substituted aliphatic acyl hydrocarbon, aroylhydrocarbon, and nitro substituted aroyl hydrocarbon radicals, saidhydrocarbon radicals having from 1 to 20 carbon atoms, and R is a.radical selected from the group consisting of aliphatic, hydroxysubstituted aliphatic, and cycle-aliphatic radicals containing from 3 to20 carbon atoms.

2. A fuel as described in claim 1 wherein R is an aliphatic radicalcontaining three carbon atoms.

3. A fuel as described in claim 2 wherein R is hydrogen.

4. A fuel as described in claim 2 wherein R is an acetyl radical.

5. A fuel as described in claim 2 wherein R is a halogenated acetylradical.

6. A fuel as described in claim 2 wherein R is a benzoyl radical.

7. A fuel as described in claim 2 wherein R is a nitro substitutedbenzoyl radical.

8. A liquid hydrocarbon fuel boiling within the gasoline rangecontaining about 3 to 5 grams per gallon of the reaction product ofdicobalt octacarbonyl and propargyl alcohol, said reaction producthaving the following formula:

wherein R is hydrogen and R is an aliphatic radical containing threecarbon atoms.

9. A liquid hydrocarbon fuel boiling within the gasoline rangecontaining about 3 to 5 grams per gallon of the 6 reaction product ofdicobalt octacarbonyl and propargyl 2,354,646 Bell Aug. 1, 1944 acetate,said reaction product having the following 2,409,167 Veltman Oct. 8,1946formula:

R-O--R'-Co (CO) OTHER REFERENCES wherein R is an aliphatic acylhydrocarbon radical con- 5 Chemistry of Metal Carbonyls, by Wender ettaining two carbon atoms and R is an aliphatic radical LAC-So 1952,Pages 1216 to 1219- containing three carbon atoms I.A.C.S., vol. 76,March 5, 1954, No 5 pages 1457 and 1458, to t th Ed'to b St b t l.References Cited in the file of this patent commumcal n o e 1 r y em erge a UNITED STATES PATENTS 10 2,087,582 Schneider July 20, 1937

1. A LIQUID HYDROCARBON FUEL BOILING WITHIN THE GASOLINE RANGECONTAINING A REACTION PRODUCT OF DICOBALT OCTACARBONYL AND AN ACETYLENICCOMPOUND, IN AN AMOUNT SUFFICIENT TO LEND ANTI-KNOCK PROPERTIES TO THEFUEL, SAID REACTION PRODUCT HAVING THE FOLLOWING GENERAL FORMULA: